Ordered hydroxy-terminated tertiarynitrogen-containing polyether-based urethane compositions



s than@ if ORDERED ROXi-l A'IED TERTIARY- NHRGGEN-CQNTAENG POLYETIER-BASED URETHANE SWOSTINS Adolfas Darnusis, Benoit, Mich., assigner to Wyandotte Chemicals Corporation, Wyandotte, Mich., a corporation of Michigan No Drawing. Filed Mar. 26, 1959, Ser. No. 862,015

16 Claims. (Cl. 26h-77.5)

The present invention relates to novel ordered hydroxy-terminated tertiary-nioogen-containing polyetherbased urethane compositions which are of special utility as bodying agents for urethane coatings, particularly when it is not desired to employ thermoplastic resins for such purpose, and which are especially useful as hydroxyterminated urethane components for two-component polyurethane coatings or corresponding one package systems which employ as the other, or diisocyanate ingredient, a blocked isocyanate.

It is an object oi the present invention to provide novel bodying agents for urethane coatings. It is a further object to provide novel and valuable ordered hydroxyterminated urethane components for polyurethane coatings systems. A further object is the provision of such compositions which are tertiary-nitrogen-containing polyether-based urethanes. Another object is the provision of such ordered urethane compositions which lend advantageous properties to polyurethane coatings in which they are employed as the hydroxy-terminated component or ingredient. Still another object of the invention is the provision of a process for the production of such ordered urethane compositions sequentially by the reaction of about one mol of polypropyleneether glycol with about two mols of a selected arylene diisocyanate, and reaction of the thus-produced isocyanate-terminated urethane with about two mols of a selected tertiary-nitrogen-containing diol, triol, or tetraol, and the products thereby produced. Other objects of the invention will become apparent hereinafter.

The foregoing and additional objects are accomplished by the provision of ordered urethane compositions (U) of the following idealized formula:

wherein R is selected from hydrogen and methyl, wherein -O-G-O- is the radical of a polypropyleneether glycol (a) having a molecular weight between about 134 and 1000, wherein Y T, is om-@ and Tl is Ocrawherein y is selected from zero and one, and wherein Q is the radical of a tertiary-nitrogen-containing polyol (b), said radical Q being the same in both occurrences and being selected from the group consisting o f:

dll Patented Aug', 14V-, 1 962 and wherein Z is an alkylene radical containing from two through six carbon atoms, wherein M is selected from H and CH3 and may be the same or different in each occurrence, wherein n is a number from zero to four, inclusive, which may be the same or different in each occurrence and wherein x is a number from zero to one, inclusive, said urethane compositions (U) being prepared sequentially by the reaction of about one molar proportion of polypropyleneether glycol (a) with about two molar proportions of arylene diisocyanate (c) selected from the group consisting of phenylene diisocyanate, tolylene diisocyanate, and diphcnylmethane-4,4diisocyanate, to produce an isocyanate-terminated polypropyleneether glycol urethane (I), and subsequent reaction of the isocyanate-terminated urethane (I) with about two molar proportions of tertiary-nitrogen-containing polyol (b) Presence of the tertiary amine nitrogen in these ordered urethane compositions is very signiiicant. It acts as a built-in catalyst, speeds up curing of polyurethane coatings embodying these ordered hydroxy-terminated urethanes as one component or ingredient, and aects favorably the properties of polyurethane coatings formed therefrom by reaction with an isocyanate-terminated component or ingredient. Properties favorably aiected are surface hardness, film toughness, solvent resistance, and abrasion resistance. Flexibility of such coatings can be readily adjusted by changing the length of the polyoxypropylene chain or chains, either in the starting polypropyleneether glycol or in the tertiary-nitrogen-containing polyol, or 4both if desired.

These ordered hydroxy-terminated tertiary-nitrogencontaining urethane compositions have certain advantages over ordinary hydroxyl-bearing materials such as polyesters and polyols. Polyurethane coatings prepared therefrom by reaction with an isocyanate-tcrminated component dry to touch upon evaporation of solvent, and have considerably less sagging tendency than polyurethane coating formulations incorporating regular polyols.

When the ordered hydroxy-terminated urethane cornpositions of the present invention .are reacted with arl isocyanate-terminated "component, the resulting polyurethane surface coatings are characterized by properties which are superior to thoseobtained from the same isocyanate component and previously known polyhydroxy components. The same is true when they are employed as one ingredient of a single component surface coating composition together with a blocked isocyanate as the other ingredient (for example, in baking enamels or wire coatings). rl`his is also true for polyurethane Ysurface coatings prepared from the ordered hydroxy-terminated urethane compositions of the invention as opposed t0 those prepared from random hydroxy-terminated urethane A reaction products, compared to which latter a higher solid content Iat lower viscosity can be Lattained in surface coatings embodying the ordered hydroxyterminated urethane compositions of the invention.'

The ordered hydroxy-terminated urethane compositions of the present invention are prepared fby reacting about one molar proportion of extending polypropylencether glycol of selected molecular weight between about 134 and 1000 and about two molar proportions of an appropriate arylene diisocyanate selected from phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, including mixtures of 2,4 and 2,6 tolylene diisocyanates, and diphenylmethane-4,4'diisocyanate, to produce a diisocyanate-terminated urethane having a free NCO group at each end of the molecule. If desired, about one molar proportion of one diisocyanate and about one molar proportion of another diisocyanate may be used. One molar proportion of this isocyanate-terminated yurethane adduct is then reacted with about two molar proportions of the selected tertiary-nitrogen-containing polyol to produce an ordered hydroxy-terminated urethane composition in which the terminal hydroxy groups are furnished Iby the tertiary-nitrogen-containing -polyol molecule.

The tertiary-nitrogen-containing polyols used in the llinal stage of the sequential reaction are selected from the following:

(1) Compounds encompassed by the formula:

wherein Z is an alkylene radical containing from two through six carbon atoms, wherein M is selected from hydrogen and methyl, and wherein n is a number from zero to four, inclusive, preferably not more than two, and wherein x is a number from zero to one, inclusive, which include, for example, N,N,N,Ntetrakis(2-hydroxypropyl) ethylene diamine, N mono(2hydroxyethyl) N,N',Ntris(2hydroxypropyl)ethylene diamine, addition product of one mol of N,N,N,Ntetrakis(Z-hydroxypropyl)ethylene diamine with one to 16 mols of propylene oxide, addition product of one mol of N,N,NNtetral is (2-hydroxypropyl)ethylene diamine with one to three mols of propylene oxide and then with one mol of ethylene oxide, addition product of one mol of N,N,N,N' tetrakis(2hydroxypropyl)ethylene diamine with four to 16 mols of propylene oxide and then with one mol of ethylene oxide, the corresponding higher alkylene diamines, such as N-mono(2hydroxyethyl)-N,N',Ntris (2-hydroxypropyl)propylene diamine, N,N,N',N'tetrakis (2-hydroxypropyl)propylene diamine, addition products of N,N,N',N tetrakis(2hydroxypropyl)propylene diamine with from one to 16 mols of propylene oxide and the monoethylene oxide further addition products thereof, the corresponding tetramethylene and hexamethylene diamines, and the N,N,N,Ntetrakis(2-hydroxypropyl) tetramethylene and hexamethylene diamine mono through hexadeca propylene oxide addition products thereof and such adducts further reacted with one mol of ethylene oxide, and the like. Addition of one mol of ethylene oxide in polyols of types l, 2, or 3 provides a primary hydroxy group of relatively high reactivity for definite direction and precedence of reaction with NCO groups in preparing the linal OH-terminated urethane from the intermediate NCQ-terminated urethane.

(2) Compounds encompassed by the formula:

CH2-CHO (CaHaO)nH CH3 Y CH3-HO (03H60) 11H wherein M is selected from hydrogen and methyl, wherein n is a number from zero to four, inclusive, preferably not more than two, and wherein x is a number from zero to one, inclusive, which include, for example, N-mono- (ethanol) N,N -,di(isopropanol)amine, triisopropanolamine, triisopropanolamine addition product with one mol of ethylene oxide, niisopropanolamine addition product with from one to 12 mols of propylene oxide, triisopropanolamine addition product with two mols of propylene (M)n M I moogHl) xtooanouo onf-CHEN wherein M is selected from hydrogen and methyl and may be the same or different in each occurrence, wherein n is a number from zero to four, inclusive, which may be the same or diiferent in each occurrence, preferably not more than two, and wherein x is a number from zero to one, inclusive, which include, for example, 1,4-bis-(2-hydroxypropyl) piperazine, 1-(2-hydroxyethyl) -4-(2-hydroxypropyl) piperazine, 1,4-bis-(2-hydroxypropyl)-methylpiperazine (including dimethyl, trimethyl, and tetramethyl piperazines), l-(2-hydroxyethyl)-4-(2-hydroxypropyl) -methylpiperazine, addition products of one mol of a 1,4-bis-(2-hydroxypropyl)-methylpiperazine with one mol of ethylene oxide, addition products of 1,4-bis-(2- hydroxypropyl) -piperazine or a 1-4-bis-(2-hydroxypropyl)-methylpiperazine with from one to eight mols of propylene oxide, addition products of 1,4-bis-(2-hydroxypropyl)-piperazine or a 1,4 bis (2-hydroxypropyl) methylpiperazine with from one to eight mols of propylene oxide and then with one mol of ethylene oxide, and the like.

'In practice, the molecular weights of the ordered hydroxy-terminated urethane compositions of the invention, prepared in this sequential manner, have been found to be very close to the molecular weight of a composition having an idealized structure, since very little side reaction occurs using predetermined molar proportions and the sequential addition procedure under moderate reaction conditions, Viz., initial reaction temperature below about 60 C. and exclusion of moisture. Also, in practice, a chain length of not `greater than about 750, and preferably about 300-400, molecular weight has been found most advantageous for the starting polypropyleneether glycol, and a tertiary-amine-nitrogen-containing polyol addition product having no more than about two propylene oxide units added per individual chain of starting polyol is preferred, as in an alkylene diamine-derived polyol. When using a polypropyleneether glycol of mnimum molecular weight, it is preferred that the polyol used contain several propylene oxide units per individual chain. As for the isocyanate employed, tolylene diisocyanate, usually a mixture of about 80%/ 20% of the 2,4 and 2,6 isomers, is preferred for reasons of economy. Other variations in the starting materials to procure variations in the substituents of the ordered hydroxy-terminated urethane compositions may be usefully made to obtain polyurethane surface coatings of varying types and characteristics upon reaction with a selected isocyanate component. For example, lengthening of the polyoxypropylene chains shown in the above formulae results in a polyurethane coating having a longer pot life, greater flexibility, and lower solvent resistance, while shortening of these polyoxypropylene chains have just the opposite eifect. The preferred equivalent weight of the hydroxy-terminated urethanes of the present invention is between about 200 K and about 400.

The following examples yare given to illustrate the present invention but are not to be construed as limiting:

Y GENERAL vPROCEDURE n 2/1 and contains two freeANCO groups. In the second stage, two molar proportions of a diol, triol or tetraol containing tertiary amine nitrogen are added to one molar proportion of the adduet in order to form a hydroxyterminated intermediate with free OH groups on both ends of the molecule. The addition of two diol molecules to the adduct changes the NCO/ OH ratio to 1/1.5; two triols to l/2.0; two tetraols to 1/2.5. Dilution of the NCC-terminated intermediate at the end of stage l may be with any suitable nonreactive surface coating solvent. Many such solvents suitable in general for urethane coatings and components thereof are known in the art, for example, 2-ethoxyethyl acetate, Z-methoxyethyl acetate, 2- butoxyethyl acetate, toluene, xylene, ethyl acetate, butyl acetate, amyl acetate, other similar esters, ketones, chlorinated solvents, nitro-aliphatic solvents, dioxane, and the like. In some instances no solvent is required during any stage of the reaction.

Polyether polyols used in the reaction are preferably stripped of water by azeotropic distillation with toluene. In this manner, the amount of water can be decreased from 0.08-015 to 0.02% or even less. A clean, dry, three-necked tive-liter ask was used as a reaction Vessel, and a nitrogen blanket was maintained over the reactants.

Noma-Ratio of reaction groups NGO/OH: 4/10 1/2.5.

Procedure:

Stage 1.-Add to the 5liter reaction vessel:

Parts Tolylene diisocyanate `696 Polypropyleneether glycol, NW. 420-(Pluracol By gradual addition of the Pluracol P-410, the temperature of the exothermic reaction is maintained below 60 C. If necessary, cooling is applied. The reactants are stirred for 2 hours at 60 C. and then diluted with:

Parts 2-ethoxyethyl acetate o1 2-butoxyethyl acetate 150 Xylene 150 Stage 2.-Add to the prepared cooled adduct all the Quadrol, blended with solvent:

Parts: Quadrol 1 168 2-ethoxyethyl acetate 430 Xylene 430 Hold the temperature below 40 C. until the exothermic reaction ceases. Then stir the reactants at 70 C. for 3 hours. Measure the viscosity after each hour of heating.

The resulting (3H-3 solution was poured into a clean, dry bottle and tightly capped to exclude moisture.

Properties:

NCO/OH l/2.5 Average molecular weight 1,352 Average equivalent weight 225.5 Hydroxyl number 249 Percent hydroxyl 7.56 Properties of OH-3 solution:

Nonvolatile, percent 70 Weight per gallon, lb 8.75

Viscosity at 25 C., cps 4,000-6,000

OH-3 in urethane coatings: Hydroxyl-termina-ted urethane OH-3 is used as the second component of urethane coatings. The iirst component consists of an isocyanateterminated intermediate. Two typical formulations are presented here.

TYVO COMPONENT URETHANE COATINGS Formulation Composition 3 NC O-B 199 OH-3 1 .2/1 .0

1 Numerous other organic polyisocyanates can be used as well as NC O-1 and NGO-., such as, for example, tri TDI adduct of trimethylolpropane or hexanetriol, the phenylurethanes of any of the foregoing, TDI, MDI, and the like.

2 NGO-1 is the NC O-terminated reaction product of three mols of TDI with one mol of TP 4-10 polyol (propylene oxide addition product of trimethylolpropane having a M.W` of about 410).

3 NGO-3 is the NGO-terminated reaction product of two mois of NC O-l with one niol of P 410 polyol (polypropylene glycol, M.W. about 420) Formulation Properties Curing time:

Dust free, hrs. 0.7- 0. 6.

Dry to touch, hrs 1.0 0.6. Pot life, hrs 0.75 1.2. Sward hardness 62 60. Elongation, percent. 4

10-20. Tensile strength, psi 7, OOO-10, 000.

Direct, inch-lbs 12-20 16-24. Indirect, inch-lhs 6-12 8-16. Abrasion resistance, Ing/1,000 cycles 10-30 20-40. Chemical resistance:

20% NaOH FYr'ellonf Excellent. 20% HNOQ dn D0. Solvent resistance, hrs.:

Toluene 4 4, 2-Ethoxyeth'yl acetate 4 4. Methyl isobutyl ketone 4 3. Water resistance:

Immersion 24 hrs. at 25 C No effect No effect. Immersion l/ hr. at 100 C do Do. Weatherometer (twin are) test, 500 hrs No loss of No loss of gloss. gloss.

Explanation: Film hardness of these two coatings is very high at a comparatively good film flexibility. Solvent resistance is better in a more branched formulation (such as 1) than in a less branched formulation (such as 2). Formulation 2 still has a solvent resistance from very good to good. Abrasion resistance is excellent. More highly branched coatings exhibit improved abrasion resistance. Elongation and impact test indicate that the coatings are semi-llexible, not brittle. Tensile strength is very high. Resistance in the weatherometer test is excellent.

Procedure: 696 parts of TDI were reacted with 2000 parts of P-10l0 at a temperature below 60 C. for at least 2 hrs. The reaction product was diluted with 216 parts of 2-ethoxyethyl acetate and 216 parts xylene.

1168 parts of Quadrol, dissolved in 61'2 parts of 2- 7 ethoxyethyl acetate and 612 parts of xylene, were then added to the P-lOlO/TDI adduct and the reactants stirred at 70 C. for 3 h rs.

Properties:

NCO/ OH l/2.5 Average molecular Weight 1932 Average .equivalent Weight 322 Hydroxyl number 174 Percent hydroxyl 5.27 Properties Vof OH-3A solution:

Nonvolatiles, percent 70 Weight per gallon, lb 8.72

Viscosity at 25 C., cps 3,000-5,000

OH-3A urethane coatings:

Formulation COMPOSITION Isocyanate-terminated intermediate NC O-l NC O-3 arts 101 162 Hydroxyl-termtuated intermediate.- OH-BA OH-SA Parts 100 10 NGO/OH 1.2/1. 1.2/1.0

PROPERTIES Curing time:

Dust free, hrs 0. 8 0.9

Dry to touch hrs. 1. 1. 6 Pot life, hrs 2.0 2. 5 Sward hardness; 60-64 56-60 Elongation, percent Up to 60 Up to 200 Impact test-Gardner: f

Direct, inch-lbs- 30 30 Indirect, inch-lbs 18 24 Solvent resistance, hrs.:

Tnlnerw 3 3 Methyl isobutyl ketone 1% 1 Chemical resistance and water immersion resistance are excellent. The OH-3A of Example 2 gives more flexible lms with a lower solvent resistance than the OH-3 of Example l. The hardness of the lms is retained at a high level.

Procedure: 696 parts of TDI were reacted with 268 parts of DPG at a temperature not over 60 C. for at least 2 hrs. The reaction product was then diluted with 156 parts lof 2-ethoxyethyl acetate and 156 parts of xylene. A 1824 parts of TIPA P-450T with 442 parts of 2- ethoxyethyl acetate and 442 parts of xylene were added to the DPG/TDI adduct and the reactants were stirred at 70 C. for 3 hrs.

Properties of OH-SB:

NCO/ OH 1/2 Average molecular Weight 1394 Average equivalent Weight 348.5 Hydroxyl number 161 Percent hydroxyl 4.90 Properties of OH-3B solution:

Nonvolatile, percent 70 Weight per gallon, 1b 8.86

Viscosity at 25 C., cps l0,000-13,000

Intermediate YOH-3B in urethane coatings:

Formulation COMPOSITION Isoeyanate-terminated intermediate NGO-1 NGO-3 N (JO-3 Parts 52. 7 83. 7 140 HydrOxyl-terminated intermediate Oli-3B OH-BB OH-BB 100 100 1.2/1 1.2/1 2/1 PROPERTIES Curing time:

Dust free, hrs 1.0 1. 0 1. 0 Dry to touch, hrs.. 1. 5 1. 5 1.6 Pot life, hrs 24 20 24 Sward hardness 42-54 42-52 40-52 Elongation, percent- 8 9-12 60-90 Tensile strength, p.s. 4, OOO-6, 000 5, 00C-8, 000 3, OOO-5,000 Impact test-Gardne Direct, inch-lbs-- 10-16 14-18 16-24 Indirect, inch-lbs 4-8 6-12 6-12 Abrasion resistance, mg./1,000

cycles 20 10-20 28 Solvent resistance:

Toluene 4 3 4 Methyl isobutyl ketone -2 1. 5 3

Chemical resistance and Water immersion resistance are excellent. The coatings prepared from OH-terminated urethane OH-3B of Example 3 exhibit a much longer, more favorable pot-life time, but are not as hard and have less solvent resistance than those prepared from the OH-3 product of Example 1.

OH3X in urethane surface coatings-When employed as the second component together with NCO-l or NCC-3 at the NCO/OH ratio 1.2/1.0, OH-3X gives hard urethane films which are less flexible but which have `greater solvent resistance than the films of Example 2. Chemical resistance, Water immersion resistance and abrasion resistance are excellent.

Example 5 (OH-3v) Reaetants Moles Parts Polypropyleneether glycol, M.W. 420 1 820 Diphenylmethane-4,4'diisocyanate (MDI) 2 1, 112 Addltion product of 4 mols of propylene oxide to one mol o f N,N,N' N -tetrakis (Zhydroxypropyl) ethylene diamine 2 2, 016 2ethoxyethy1 acetate 846 Xylenn 846 Procedure: Same as in Examples 1-3.

OH-3Y in urethane surface coatings: When employed as the second component together with NCO-l or NCC-3 at the NCC/OH ratio 1.2/1.0, OH-3Y gives urethane films which are more llexible but which have less solvent resistance than the films of Example l. Chemical resistance and water immersion resistance I`are excellent.

Properties:

NCC/OH 1/2.0 Average molecular W Average equivalent Weight 392 Hydroxyl number 143 Percent hydroxyl 4.34

Oli-3D in urethane surface coatings: When employed as the second component together with NGO-1 or NGO-3 at the NGO/OH ratio 1.2/ 1.0, (EH-3D gives urethane films which are more ilexihle but which have less solvent resistance than the films of Example 1. Chemical resistance and Water immersion resistance are excellent.

Example 6 Example 9 (OH-sz) (0H-3Q) Reactants Mols Parts Reactants Mols Parts D' le e 1 1 1 536 Dipropylene glycol 1 134 Tigiilg/zli 2,2/2?) 2 1, 292 20 Tor genoom/2,6) 2 34s 1,4-bis-(2-hydroxypropyl)methylp er 2 1, '728 Addltion product of 1 mol o propylene oxide and zethoxyethyq acetate 784 then one mol of ethylene oxide to one mol of XylemA 784 1,4bis-(2-hydroxy'propyD-piperazine 2 636 Q-ethoxyethyl acetato 240 Xylene 24() Procedure: Same as in Examples 1-3. 2 Properties; D Procedure: Same as in Examples 1 3.

Neo/OH 1/1.5 P mpees: Average molecular welght 910 NGO/OH 1/15 Average eqmvalent Welght 455 Average molecular Weight 1118 Hydfoxyl Dumber 121 30 'Average equivalent weight 559 Percent hydroxyl- 3-7 Hydroxyl number 10() OH-3Z in urethane surface coatings: When employed Percent hydroxyl 3.04

as the second component together with NCO-l or NGO-3 at the NCO/OH ratio 1.2/1.0, OH-3Z gives urethane ilrns which are more exible but which have less solvent resistance than the lilms of Example 1. Chemical resistance and water immersion resistance are excellent.

OH-3P in urethane surface coatings: When employed as the second component together with NCO-l or NGO-3 at the ratio NCO/OH=1.2/ 1.0, OH-3P gives urethane lms which are flexible and have a good solvent resistance. The formulation has a longer pot-life time than the formulation of Example 2. Chemical resistance and Water immersion resistance are good.

Example 8 (OH-3D) Reactants Mols Parts Polypropyleneether glycol; M.W. 750 1 1, 500 TDI (2,41 2 696 Addition product of one mol of ehtylene oxide to triisopronannlamino 2 940 2fethoxyethyl ace'fft 397 Xylcno 397 Procedure: Same as in Examples 1-3.

(JH-3Q in urethane surface coatings: When employed as the second component together with NCO-l or NCC-3 at the NCC/OH ration 1.2/ 1.0, OH-3Q gives urethane films which are more flexible but which have less solvent resistance than the lms of Example 1. Chemical resistance and Water immersion resistance are excellent.

OH-3L in urethane surface coatings: When employed as the second component together with NCO-l or NCQ-3 at the NGO/OH ratio 1.2/1.0, OH-3L gives urethane lms which are more flexible but which have less solvent resistance than the films of Example 1. Chemical resistance and water immersion resistance are excellent.

Example 11 (OH-3M Reactants Mols Parts Polypropyleneether glycol, M.W. 750 1 1, 500 TDI (8D/20; 2,4/2,6) 2 606 N- (Z-hydroxyethyl) -N N-di (2fhydroxypropyl) amine- 2 708 2ethoxyethyl acetate 363 Xylono 363 Procedure: Same asin Examples 1-3.

1 1 Properties:

NCO/ OH 1/ 2.0 Average molecular weight 1450 Average equivalent weight 362 Hydroxyl number 155 Percent hydroxyl 4.6

OH-3M in urethane surface coatings: When employed as the second component together with NCO-l or NGO-3 at the NCC/OH ratio 1.2/1.0, OH-3M gives urethane films which are more exible but which have less solvent resistance than the lms of Example 1. Chemical resistance and water immersion resistance are excellent.

OH-3N in urethane surface coatings: When employed as the second component together with NCQ-1 or NGO-3 -at the NCO/OH ratio 1.2/1.0, OH-3N gives urethane lms which are less flexible but which have greater solvent resistance than the films of Example 1. Chemical resistance and Water immersion resistance are excellent.

I=t is to be understood that the invention is not to be limited to the exact details of operation or exact compounds shown and described, as obvious modifications and equivalents will be apparent to one skilled in the art, and the invention is therefore to be limited only by the scope ofthe appended claims.

I claim:

1. An ordered hydroxy-terminated urethane composition produced sequentially by rst mixing and reacting together about one molar proportion of polypropyleneether glycol (a) with about two molar proportions of arylene diisocyanate (c) selected from the group consisting of phenylene diisocyanate, tolylene diisocyanate, and diphenylmethane4,4-diisocyanate, to produce an isocyanate-terminated polypropyleneether glycol urethane, and then mixing and reacting about one molar proportion of the thus-formed isocyanate-terminated urethane with about two molar proportions of tertiary-nitrogen-containing polyol (b), said tertiary-nitrogen-containing polyol (b) being selected lfrom the group consisting of polyols of the formulae:

l N-CHz-CHO (CalEIaOhH l2 wherein Z is lan alkylene radical containing from 2 through 6 carbon atoms, wherein M is selected from H and CH3, wherein n :is a number from zero to four, inclusive, and wherein x is zero |to one, inclusive, to produce the desired ordered hydroxy-'terminated urethane composition, the initial reaction temperature in the first step of the reaction being not greater than about sixty degrees centigrade.

2. A ordered.hydroxy-terminated urethane composition according to claim 1 wherein the polypropyleneether glycol (a) has a molecular weight not greater than about 750 and n does not exceed two.

3. An ordered hydroxy-terminated urethane composition according to claim 2, wherein the arylene diisocyanate (c) is tolylene diisocyanate and the tertiary-nitrogen-containing polyol (b) is an alkylene oxide addition product of ethylene diamine.

4. An ordered hydroxy-terminated urethane composition according to claim 2 wherein the `arylene diisocyanate (c) is tolylene diisocyanate and the tertiary-nitrogen-containing polyol (b) is a triisopropanolamine alkylene oxide addition product.

5. An ordered hydroxy-terminated urethane composition according to claim 2 lwherein the arylene diisocyanate (c) is tolylene diisocyanate and the tertiary-nitrogen-containing polyol (b) is a 1,4-bis-(2-hydroxypropyl)-piperazine alkylene oxide addition product.

6. An ordered hydroxy-terminated urethane composition according to claim 1 wherein the average equivalent weight is between about 200 and about 500.

7. A solution of an ordered hydroxy-terminated urethane composition according to claim l in a surface coating solvent which is nonreactive therewith.

8. A urethane coating composition including as one component an ordered hydroxy-terminated urethane composition according to claim 1 and including an organic polyisocyanate as a second component.

9. A coating composition according to claim 8, including an organic surface coating solvent which is nonreactive with both the components of the coating composition and their polyurethane reaction product.

10. A process for the sequential production of an ordered hydroxy-terminated urethane composition which. includes the steps of -rst mixing and reacting togetherV about one molar proportion of polypropylene-ether glycol (a) with about two molar proportions of arylene diisocyanate (c) selected from the group consisting of phenylene diisocyanate, tolylene diisocyanate, and diphenylmethane-4,4-diisocyanate, to produce an isocyanate-terminated polypropyleneether glycol urethane, and then mixing and reacting about one molar proportion of the thus-formed isocyanate-terrninated urethane with about two molar proportions of tertiary-nitrogen containing polyol (b), said tertiary-nitrogen containing polyol (b) being selected from the group consisting of polyols of the formulae:

13 and wherein Z is an alkylene radical containing from 2 through 6 carbon atoms, wherein M is selected from H and CH3, wherein n is a number from zero to four, i11- wherein Z is an alkylene radical containing from 2 through N--CHz-CHO (CaHnOnH) 6 carbon atoms, wherein M is selected from H and CH3, wherein n is a number from zero to four, inclusive, and

wherein x is zero to one, inclusive.

clusive, and wherein x is zero to one, inclusive, to produce the desired ordered hydroxy-terminated urethane composition, the initial reaction temperature in the rst step of the reaction being not greater than about sixty degrees centigrade.

11. A process for producing an ordered hydroxy-terminated urethane composition according to claim 10, 15 portions of arylene diisocyanate (c) selected from the wherein the polypropyleneether glycol (a) has a molecugroup consisting of phenylene diisocyanate, tolylene dilar weight not greater than about 750 and n does not isocyanate, and diphenylmethane-4,4diisocyanate, to exceed two. produce an isocyanate-terminated polypropyleneether gly- 12. A process for producing an ordered hydroxy-tercol urethane (I), and then mixing and reacting about one minated urethane composition according to claim 11, molar proportion of the thus formed isocyanate-termiwherein the arylene diisocyanate (c) is tolylene diisocyanate and the tertiary-nitrogen-containing polyol (b) is an alkylene oxide addition product of ethylene diamine.

13. A process for producing an ordered hydroxy-ternated urethane (I) with about two molar proportions of tertiary-nitrogen-containing polyol (b), selected from the group consisting of:

minated urethane composition according to claim 11,

wherein the arylene diisocyanate (c) is tolylene diisocy- (l) CH3 anate and the tertiary-nitrogen-containing polyol (b) is a I triisopropanolamine alkylene oxide addition product. Il CH2-CHO(C3HO)H 14. A process for producing an ordered hydroxy-ter- H-(OCzHQAOoaHnooH-oHz-N CH3 minated urethane composition according to claim 11, CHrCHoaHunH wherein the arylene diisocyanate (c) is tolylene diisocyanate and the tertiary-nitrogen-containing polyol (b) is a 1,4-bis-(2-hydroxypropyl)-piperazine alkylene oxide addition product.

15. An ordered tertiary amine nitrogen-containing hydroxy-terminated urethane composition prepared by and rst mixing and reacting about one molar proportion of (2) tlHs CH: polypropyleneether glycol (a), having a molecular weight H(0C,H)0CH CH, CHTCHMCSHOMH between about 134 `and 1000, with about two molar proportions of arylene diisocyanate (c) selected from the lia N-Z-N CH group consisting of phenylene diisocyanate, tolylene di- H-(0C2H4)x(0CsH)nOCH-C 1 CHz-CHOwaHoOhH isocyanate, and diphenylmethane-4,4diisocyanate, to produce an isocyanate-terminated polypropyleneether glycol urethane (I), and then mixing and reacting about one and (3) M (Mh CHs molar proportion of the thus-formed isocyanate-terminated urethane (I) with about two molar proportions of tertiary-nitrogen-containing polyol (b) selected from the group consisting of:

CH (D l 3 55 References Cited in the le of this patent M GHz-onoannn UNITED STATES PATENTS H-(OCQH4),(OCaHmoCH-om-N CH,

CHT-HNOSHMH 2,814,605 stnmar Nov. 26, 1957 and 2,915,496 Swart et al. Dec. 1, 1959 (2) o o CH CH o C H o H FOREIGN PATENTS H( 03H0 2' 3 206,295 Australia Feb. 1o, 1955 lll/I N-Z-N (IJHa H-(oonrnxcanonooH-CH, Y onr-cnorcaneohn OTHER REFERENCES and Chemical and Engineering News, January 21, 1957, (3) (mn page 78.

M E. I. du Pont de Nemours and Co., Wilmington, Del.,

wherein Z is an alkylene radical containing from 2 through 6 carbon atoms, wherein M is selected from H and CH3, wherein n is a number from zero to four, in-

clusive, and wherein x is zero to one, inclusive.

Continuous Preparation of Urethane Foam Prepolymer, H11-29, July 1958.

UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTIUN Patent No.` 3,049,514 August 14, 1962 Adolfas Damusis It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 4, line 61, for "have" read has column 9, Example 8, in the table, first column, line 3 thereof, for "ehtylene" read ethylene column 10, line 35, for "ration" read ratio column 11, line 6T, formula (2) for second occurrence, read same column 11, line '75, lefthmid portion of formula (3) for "H-(OC2H3)" read H-(OC2H4) column 12, line 8, for "A" read An column 13, line 4, right-hand portion of formula (3) for "CHO'CC3H60nH)" read -CHO(C3H6O)nH Signed and sealed this 16th day of Apri1 1963.

(SEAL) Attest:

DAVID L. LADD ERNEST W. SWIDER Commissioner of Patents Attesting Officer 

1. AN ORDERED HYDROXY-TERMINATED URETHANE COMPOSITION PRODUCED SEQUENTIALLY BY FIRST MIXING AND REACTING TOGETHER ABOUT ONE MOLAR PROPORTION OF POLYPROPYLENEETHER GLYCOL (A) WITH ABOUT TWO MOLAR PROPORTIONS OF ARYLENE DIISOCYANATE (C) SELECTED FROM THE GROUP CONSISTING OF PHENYLENE DIISOCYANATE, TOLYLENE DIISOCYANATE, AND DIPHENYLMETHANE-4,4''-DIISOCYANATE, TO PRODUCE AN ISOCYANATE-TERMINATED POLYPROPYLENEETHER GLYCOL URETHANE, AND THEN MIXING AND REACTING ABOUT ONE MOLAR PROPORTION OF THE THUS-FORMED ISOCYANATE-TERMINATED URETHANE WITH ABOUT TWO MOLAR PROPORTIONS OF TERIARY-NITROGEN-CONTAINING POLYOL (B), SAID TERTIARY-NITROGEN-CONTAINING POLYOL (B) BEING SELECTED FROM THE GROUP CONSISTING OF POLYOLS OF THE FORMULAE: 